JP6108015B2 - Method for reducing modulus of cured silicone rubber, and silicone rubber composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a method for reducing the modulus of a cured silicone rubber, and in particular, the cured rubber has a low modulus, and curing of an addition-curable silicone rubber composition useful for electrical, electronic, automotive, precision machine, construction, etc. The present invention relates to a method for reducing the modulus of a cured silicone rubber that can provide a product, and a silicone rubber composition.

  In recent years, taking advantage of the properties of silicone rubber, its application has expanded in the fields of electricity, electronics, automobiles, construction, etc. Especially, it has excellent heat resistance, weather resistance, oil resistance, cold resistance, electrical insulation, etc. It is an effective means for manufacturing seal members for parts and consumer parts.

  Many reports have been made on reducing the modulus of addition-type heat-curable silicone rubber compositions. For example, it is known to add a non-functional oil in order to lower the modulus of a cured silicone rubber. However, the addition of non-functional oil reduces the rubber hardness and modulus, but the non-functional oil bleeds on the surface of the cured rubber. In addition, there is a drawback that the adhesiveness is inhibited when cured. On the other hand, there is a method of reducing the addition amount of the inorganic filler as another method of lowering the modulus, but in this case, the strength of the cured rubber is also reduced, so that there is a drawback that it is limited to special potting and other uses. . Addition of an organopolysiloxane having an average of one alkenyl group bonded to a silicon atom in one molecule may cause adhesion inhibition when cured, contaminate contacted materials after curing, or shrink A curable silicone rubber composition and its cured product (Patent Document 1: Japanese Patent Laid-Open No. 3-52956) and the like that do not cause defects such as a change in shape are proposed.

  However, in order to reduce the modulus of a high hardness, high strength silicone rubber composition, the composition as proposed above does not meet user requirements, and it has a high hardness suitable for sealing members for automotive parts and consumer parts. Therefore, it has been strongly desired to provide a silicone rubber composition having high strength and low modulus.

Japanese Patent Laid-Open No. 3-52956

  The present invention has been made in view of the above circumstances, and a cured silicone rubber that can provide a cured silicone rubber having high hardness, high strength, and low modulus suitable for sealing members for automotive parts and consumer parts. It is an object of the present invention to provide a method and a silicone rubber composition for reducing the modulus.

  As a result of intensive studies in order to achieve the above object, the present inventors have found that an addition-curable silicone rubber composition containing a specific organopolysiloxane is suitable for sealing members for automotive parts and consumer parts. The present inventors have found that a cured silicone rubber having high hardness, high strength, and low modulus can be obtained.

（ｎは１〜４である。）
〔４〕
（Ａ）下記平均組成式（１）
Ｒ¹ _aＲ² _bＳｉＯ_(4-a-b)/2 （１）
（式中、Ｒ¹はアルケニル基を示し、Ｒ²は脂肪族不飽和結合を有しない非置換又は置換の１価炭化水素基を示し、ａは０．０００１〜０．２を満たす正数であり、ｂは１．７〜２．２を満たす正数であり、但しａ＋ｂは１．９〜２．４を満たす正数である。）
で示され、ケイ素原子に結合したアルケニル基を１分子中に少なくとも２個有するオルガノポリシロキサンであり、互いに組成が異なる２種のオルガノポリシロキサン（Ａ−１）及び（Ａ−２）を含むオルガノポリシロキサン混合物であって、該オルガノポリシロキサン混合物に含まれる前記２種のオルガノポリシロキサンのうち、（Ａ−１）成分は平均組成式（１）においてＲ²中にフェニル基を含まないものであり、（Ａ−２）成分は平均組成式（１）においてＲ²中にフェニル基を１〜３０モル％含有するものであるオルガノポリシロキサンであり、（Ａ−１）成分と（Ａ−２）成分との質量比が（Ａ−１）：（Ａ−２）＝９９．９：０．１〜８５：１５（合計で１００）である混合物：１００質量部、
（Ｂ）下記平均組成式（２）
Ｒ⁴ _dＨ_eＳｉＯ_(4-d-e)/2 （２）
（式中、Ｒ⁴は炭素数１〜１０の非置換又はハロゲン置換の１価炭化水素基であり、ｄは０．７〜２．１、ｅは０．００１〜１．０、ｄ＋ｅが０．８〜３．０を満足する正数である。）
で示され、１分子中に少なくとも２個のケイ素原子結合水素原子を含有するオルガノハイドロジェンポリシロキサン：本成分中に含まれるケイ素原子に結合した水素原子の数が（Ａ）成分中のケイ素原子結合アルケニル基１個当たり１〜５個となる量、
（Ｃ）補強性シリカ微粉末：１〜１００質量部、
（Ｄ）付加反応触媒：触媒量、
（Ｅ）オルガノポリシロキサン中のケイ素原子に結合した１価の有機基の２０〜７０モル％がフェニル基であり、フェニル基以外のケイ素原子に結合する１価の有機基が炭素数１〜６のアルキル基であり、２５℃での粘度が回転粘度計による測定で１５０〜４５０ｍＰａ・ｓである無官能性シリコーンオイル：０．５〜２０質量部
を含有してなり、かつ上記（Ａ−１）成分と（Ａ−２）成分との混合物からなる（Ａ）成分の２５℃での粘度が回転粘度計による測定で５０〜１００，０００ｍＰａ・ｓであり、（Ａ−２）成分の２５℃での粘度が回転粘度計による測定で５０〜１，０００ｍＰａ・ｓであるシリコーンゴム組成物。
〔５〕
更に、（Ｆ）１分子中に少なくとも１個のＳｉＨ基と、少なくとも１個のフェニレン骨格を有する有機ケイ素化合物を接着性付与成分として（Ａ）成分１００質量部に対して０．１〜３０質量部を含有する〔４〕に記載のシリコーンゴム組成物。
〔６〕
接着性付与成分が、下記式で示される化合物から選ばれる〔５〕に記載のシリコーンゴム組成物。

（ｎは１〜４である。） Accordingly, the present invention provides a method and silicone rubber composition for reducing the modulus of the cured silicone rubber described below.
[1]
(A) The following average composition formula (1)
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ represents an alkenyl group, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is a positive number satisfying 0.0001 to 0.2. Yes, b is a positive number satisfying 1.7 to 2.2, provided that a + b is a positive number satisfying 1.9 to 2.4.
An organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having two different organopolysiloxanes (A-1) and (A-2) having different compositions Among the two types of organopolysiloxanes contained in the organopolysiloxane mixture, the (A-1) component does not contain a phenyl group in R ² in the average composition formula (1). The component (A-2) is an organopolysiloxane containing 1 to 30 mol% of a phenyl group in R ² in the average composition formula (1), and the components (A-1) and (A-2) ) Mixture in which the mass ratio to the component is (A-1) :( A-2) = 99.9: 0.1-85: 15 (100 in total): 100 parts by mass,
(B) The following average composition formula (2)
_{^{R 4 d H e SiO (4}} -de) / 2 (2)
(In the formula, R ⁴ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, d is 0.7 to 2.1, e is 0.001 to 1.0, and d + e is 0. A positive number satisfying .8 to 3.0.)
And an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule: the number of hydrogen atoms bonded to the silicon atoms contained in this component is the silicon atom in component (A) An amount of 1 to 5 per bonded alkenyl group,
(C) Reinforcing silica fine powder: 1 to 100 parts by mass,
(D) addition reaction catalyst: catalyst amount,
(E) 20 to 70 mol% of monovalent organic groups bonded to silicon atoms in the organopolysiloxane are phenyl groups, and monovalent organic groups bonded to silicon atoms other than phenyl groups are 1 to 6 carbon atoms. A non-functional silicone oil having a viscosity at 25 ° C. of 150 to 450 mPa · s as measured by a rotational viscometer: 0.5 to 20 parts by mass, and the above (A− The viscosity at 25 ° C. of component (A) comprising a mixture of 1) component and (A-2) component is 50 to 100,000 mPa · s as measured by a rotational viscometer, and 25 of component (A-2) A silicone rubber composition having a viscosity at 50 ° C. measured by a rotational viscometer of 50 to 1,000 mPa · s is prepared, and the composition is heat-cured, as defined in JIS K 6249 of a cured silicone rubber. 100% A method of reducing the Jurasu.
[2]
Further, (F) an organosilicon compound having at least one SiH group and at least one phenylene skeleton in one molecule is used as an adhesion-imparting component, and 0.1 to 30 masses per 100 mass parts of component (A). [1] The method according to [1].
[3]
The method according to [2], wherein the adhesion-imparting component is selected from compounds represented by the following formula.

(N is 1-4)
[4]
(A) The following average composition formula (1)
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ represents an alkenyl group, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is a positive number satisfying 0.0001 to 0.2. Yes, b is a positive number satisfying 1.7 to 2.2, provided that a + b is a positive number satisfying 1.9 to 2.4.
An organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having two different organopolysiloxanes (A-1) and (A-2) having different compositions Among the two types of organopolysiloxanes contained in the organopolysiloxane mixture, the (A-1) component does not contain a phenyl group in R ² in the average composition formula (1). The component (A-2) is an organopolysiloxane containing 1 to 30 mol% of a phenyl group in R ² in the average composition formula (1), and the components (A-1) and (A-2) ) Mixture in which the mass ratio to the component is (A-1) :( A-2) = 99.9: 0.1-85: 15 (100 in total): 100 parts by mass,
(B) The following average composition formula (2)
_{^{R 4 d H e SiO (4}} -de) / 2 (2)
(In the formula, R ⁴ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, d is 0.7 to 2.1, e is 0.001 to 1.0, and d + e is 0. A positive number satisfying .8 to 3.0.)
And an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule: the number of hydrogen atoms bonded to the silicon atoms contained in this component is the silicon atom in component (A) An amount of 1 to 5 per bonded alkenyl group,
(C) Reinforcing silica fine powder: 1 to 100 parts by mass,
(D) addition reaction catalyst: catalyst amount,
(E) 20 to 70 mol% of monovalent organic groups bonded to silicon atoms in the organopolysiloxane are phenyl groups, and monovalent organic groups bonded to silicon atoms other than phenyl groups are 1 to 6 carbon atoms. A non-functional silicone oil having a viscosity at 25 ° C. of 150 to 450 mPa · s as measured by a rotational viscometer: 0.5 to 20 parts by mass, and the above (A− The viscosity at 25 ° C. of component (A) comprising a mixture of 1) component and (A-2) component is 50 to 100,000 mPa · s as measured by a rotational viscometer, and 25 of component (A-2) A silicone rubber composition having a viscosity at 50 ° C. of 50 to 1,000 mPa · s as measured by a rotational viscometer.
[5]
Further, (F) an organosilicon compound having at least one SiH group and at least one phenylene skeleton in one molecule is used as an adhesion-imparting component, and 0.1 to 30 masses per 100 mass parts of component (A). Silicone rubber composition as described in [4] containing a part.
[6]
The silicone rubber composition according to [5], wherein the adhesion-imparting component is selected from compounds represented by the following formula.

(N is 1-4)

  According to the present invention, there is provided a method capable of providing a cured product of a silicone rubber composition that has high hardness, high strength, and low modulus and is useful for electrical, electronic, automobile, precision machine, construction, and the like. .

Hereinafter, the present invention will be described in more detail.
First, the organopolysiloxane mixture of component (A) has the following average composition formula (1)
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ represents an alkenyl group, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is a positive number satisfying 0.0001 to 0.2. Yes, b is a positive number satisfying 1.7 to 2.2, provided that a + b is a positive number satisfying 1.9 to 2.4.
Among the organopolysiloxanes having at least two alkenyl groups bonded to silicon atoms in one molecule, and having two different organopolysiloxanes (A-1) and (A-2) Among the two types of organopolysiloxanes contained in the organopolysiloxane mixture, the (A-1) component does not contain a phenyl group in R ² in the average composition formula (1). There is an organopolysiloxane mixture in which 1 to 30 mol% of phenyl group in R ^2, in particular containing 2 to 30 mol% in component (a-2) has an average composition formula (1). Accordingly, both the component (A-1) and the component (A-2) are those represented by the average composition formula (1), respectively, and the components (A-1) and (A-2) The organopolysiloxane mixture of the entire component (A) as a mixture of (1) is also represented by the average composition formula (1). Note that the composition of the two types of organopolysiloxanes (A-1) and (A-2) is different from at least one of R ¹ , R ² , a, and b in the average composition formula (1). Refers to different organopolysiloxanes. Thus, when at least one of R ¹ , R ² , a, and b in the average composition formula (1) is different, an organopolysiloxane mixture containing two types of organopolysiloxanes is obtained. Hereinafter, the organopolysiloxane contained in the organopolysiloxane mixture will be described in detail.

[(A) component]
(A-1) component, (A-2) component, each organopolysiloxane, and a mixture of (A-1) component and (A-2) component (A ) Organopolysiloxane mixture as a whole component) has the following average composition formula (1)
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ represents an alkenyl group, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is a positive number satisfying 0.0001 to 0.2. Yes, b is a positive number satisfying 1.7 to 2.2, provided that a + b is a positive number satisfying 1.9 to 2.4.
And having at least two alkenyl groups bonded to silicon atoms (hereinafter also referred to as “silicon atom-bonded alkenyl groups”) in one molecule. The alkenyl group is derived from R ¹ in the above average composition formula (1), more preferably 2 to 50, and particularly preferably 2 to 20 in one molecule. These alkenyl groups may be bonded to the silicon atom at the end of the molecular chain, bonded to the silicon atom at the non-terminal end of the molecular chain (that is, other than both ends of the molecular chain), or a combination thereof. Good.

In the average composition formula (1), R ¹ represents an alkenyl group, and is not particularly limited, but preferably represents an alkenyl group having 2 to 6 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms. . Specific examples thereof include lower alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and isobutenyl group, with vinyl group being particularly preferred.

In the above average composition formula (1), R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and is not particularly limited, but preferably has 1 to 10 carbon atoms, more preferably An unsubstituted or substituted monovalent hydrocarbon group not having an aliphatic unsaturated bond having 1 to 6 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, Alkyl groups such as dodecyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; some or all of hydrogen atoms of these groups are , A group substituted with a halogen atom such as fluorine and chlorine, a chloromethyl group, a 3,3,3-trifluoropropyl group, and the like. From the viewpoint of ease of synthesis, an alkyl group and an aryl group are preferable. 3,3,3-trifluoropropyl group, more preferably methyl group, phenyl group, 3,3,3-trifluoro group Propyl group is preferred. Also, R ² in (A-1) of the two organopolysiloxane contained in the organopolysiloxane mixture is free of phenyl group, R ² of (A-2) contains a phenyl group.

  In the average composition formula (1), a is a positive number satisfying 0.0001 to 0.2, preferably a positive number satisfying 0.0005 to 0.1, and b is 1.7 to 2.2. Is a positive number satisfying 1.9, and preferably a positive number satisfying 1.9 to 2.0. However, a + b is a positive number satisfying 1.9 to 2.4, and preferably a positive number satisfying 1.95 to 2.05. If a is less than 0.0001, a cured product cannot be obtained from the silicone composition, and if it exceeds 0.2, the surface of the cured product becomes dense and a good cured product cannot be obtained, so the object of the present invention cannot be achieved. . On the other hand, when b is less than 1.7 or greater than 2.2, a stable cured product cannot be obtained from the silicone composition, and thus the object of the present invention cannot be achieved.

  The organopolysiloxane (component (A-1) and component (A-2) and the whole component (A) as a mixture thereof) is 0.00001 to 0.01 mol / g, particularly 0.00002. It preferably contains ˜0.002 mol / g alkenyl group. If the alkenyl group content is too low, the resulting composition may be inferior in curability, and if it is too high, hardness variations (dense parts) may occur on the surface of the cured silicone rubber.

The molecular structure of the organopolysiloxane according to the present invention is not particularly limited, and is a SiO ₂ unit, R ¹ SiO _3/2 unit, R ² SiO _3/2 unit, R ¹ ₂ SiO _2/2 unit, R ¹ R ^2. SiO _2/2 unit, R ² ₂ SiO _2/2 unit, R ¹ ₃ SiO _1/2 unit, R ¹ ₂ R ² SiO _1/2 unit, R ¹ R ² ₂ SiO _1/2 unit, R ² ₃ SiO Linear, branched, cyclic, three-dimensional network (resinous), etc. containing _1/2 units (wherein the groups represented by R ¹ and R ² are as defined above) Any of these may be used, but usually the main chain basically _consists of repeating diorganosiloxane units (R ¹ ₂ SiO _2/2 units, R ¹ R ² SiO _2/2 units, R ² ₂ SiO _2/2 units). Both ends of the molecular chain are triorganosiloxane units (R ¹ ₃ SiO _1/2 units, R ¹ ₂ R ² SiO _1/2 units, R ¹ R ² ₂ SiO _1/2 units, R ² ₃ SiO _1/2 units ) Chained linear diorganopolysiloxane is preferred.

  The viscosity of the organopolysiloxane according to the present invention (the (A-1) component and the (A-2) component, and the entire (A) component as a mixture thereof) is not particularly limited, but is preferably at room temperature (25 ° C.). Is 50 to 100,000 mPa · s, more preferably 100 to 10,000 mPa · s. When the viscosity is 50 to 100,000 mPa · s, the cured product obtained by curing the silicone composition of the present invention is excellent in hardness, strength, and low modulus. In the case of the component (A-2), the viscosity is more preferably about 50 to 1,000 mPa · s, particularly about 100 to 500 mPa · s. In the present invention, the viscosity can be measured with a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, etc.).

  Furthermore, the average degree of polymerization of the organopolysiloxane is preferably 25 to 1,200, particularly preferably 30 to 700. This average degree of polymerization can be determined as a weight average degree of polymerization (or weight average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis using toluene as a developing solvent.

（式中、Ｒ³は、同一又は異なる、非置換又は置換の１価炭化水素基を示し、Ｒ³の少なくとも２個はアルケニル基であり、ｃは２０〜２，０００の整数である。）
で示されるものが挙げられる。この式（１ａ）中、Ｒ³で示される非置換又は置換の１価炭化水素基は、前記Ｒ¹（アルケニル基）及びＲ²（脂肪族不飽和結合を有しない非置換又は置換の１価炭化水素基）で定義したものと同じであり、その炭素数、具体例等も同じである。また、ｃは、好ましくは２５〜１，２００、より好ましくは３０〜７００の整数である。特に、（Ａ−１）成分としては、ｃの範囲が４０〜１，２００、更には、５０〜７００程度の整数であることが好ましく、（Ａ−２）成分としては、ｃの範囲が２５〜５００、特には３０〜４００程度の整数であることが好ましい。 Examples of the organopolysiloxane according to the present invention that satisfies the above requirements include the following general formula (1a):

(In the formula, R ³ represents the same or different, unsubstituted or substituted monovalent hydrocarbon group, at least two of R ³ are alkenyl groups, and c is an integer of 20 to 2,000.)
The thing shown by is mentioned. In this formula (1a), 1 monovalent hydrocarbon radical unsubstituted or substituted represented by R ^3, the R ¹ (alkenyl group) and R ² (1 monovalent unsubstituted or substituted no aliphatic unsaturated bonds The same as that defined in (Hydrocarbon group), and the carbon number and specific examples thereof are also the same. C is an integer of preferably 25 to 1,200, more preferably 30 to 700. In particular, as the component (A-1), the range of c is preferably an integer of about 40 to 1,200, more preferably about 50 to 700, and as the component (A-2), the range of c is 25. It is preferably an integer of about 500, particularly about 30 to 400.

  Specific examples of the organopolysiloxane represented by the above formula (1a) include, as the component (A-1), molecular chain both ends dimethylvinylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane methyl. Vinylsiloxane copolymer, molecular chain one-end trimethylsiloxy group / one-end dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both-end dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, etc. As the component (A-2), molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / phenylmethylsiloxane copolymer And the like.

  The mixing ratio of the organopolysiloxanes of the two types (A-1) and (A-2) having different compositions is not particularly limited. For example, 80 to 99.99 parts by mass of the organopolysiloxane of the component (A-1) The component (A-2) can be mixed in an amount of 0.01 to 20 parts by mass, particularly preferably (A-1) so that the total of the component (A-2) and the component (A-1) is 100 parts by mass. 85 to 99.9 parts by mass of the organopolysiloxane of component (A-1) and organopolysiloxane of component (A-2) so that the total of the component and component (A-2) is 100 parts by mass. 0.1 to 15 parts by mass, more preferably 90 to 99 parts of the organopolysiloxane of component (A-1) so that the total of component (A-1) and component (A-2) is 100 parts by mass. Part by mass, (A-2) component organopolysiloxane It can be mixed in a ratio of 1 to 10 parts by weight.

  In addition, the component (A-2) is such that the ratio of diphenylsiloxane units or phenylmethylsiloxane units contained in the molecule is 1 to 30 mol% of the total siloxane units including the units at both ends of the molecular chain, particularly 2 to 2. It is preferably 30 mol% of a dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer having both ends of a molecular chain or a dimethylsiloxane / methylphenylsiloxane copolymer having both ends of a molecular chain dimethylvinylsiloxy group.

[Component (B)]
The (B) component organohydrogenpolysiloxane reacts with the (A) component and acts as a cross-linking agent, and there is no particular limitation on the molecular structure thereof. For example, linear, cyclic, Various types such as branched and three-dimensional network (resin-like) can be used, but hydrogen atoms (hydrosilyl group represented by SiH) bonded to at least 2, preferably 3 or more silicon atoms in one molecule. ), And substantially does not contain a hydroxyl group bonded to a silicon atom (ie, silanol group) in the molecule, usually 2 to 300, preferably 3 to 200, more preferably It is desirable to have about 4 to 100 SiH groups. The (B) component organohydrogenpolysiloxane may be used alone or in combination of two or more. In addition, the organosilicon compound which has an epoxy group mentioned later as organohydrogenpolysiloxane of (B) component is remove | excluded.

As the organohydrogenpolysiloxane, those represented by the following average composition formula (2) can be used.
^{_{R 4 d H e SiO (4}} -de) / 2 (2)

In the above formula (2), R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group bonded to a silicon atom, preferably having 1 to 10 carbon atoms, excluding the same or different aliphatic unsaturated bonds. As the unsubstituted or substituted monovalent hydrocarbon group in R ⁴ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl Group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, Those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., such as chloromethyl group, chloropropyl group, Examples include a bromoethyl group and a trifluoropropyl group. The unsubstituted or substituted monovalent hydrocarbon group for R ⁴ is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group. D is 0.7 to 2.1, e is 0.001 to 1.0, and d + e is a positive number satisfying 0.8 to 3.0, preferably d is 1.0 to 2 0.0 and e are 0.01 to 1.0, and d + e is 1.5 to 2.5.

  SiH groups containing at least 2 (usually 2 to 300), preferably 3 or more (for example, 3 to 200), more preferably about 4 to 100 in one molecule are represented by molecular chain terminal, molecular chain It may be located anywhere in the middle, or may be located in both. The organohydrogenpolysiloxane is preferably 0.001 to 0.02 mol / g, more preferably 0.002 to 0.015 mol / g, and still more preferably 0.003 to 0.010 mol / g. It is desirable to contain the SiH group. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures, but the number of silicon atoms in one molecule (or the degree of polymerization) is Usually 2 to 300, preferably 3 to 150, more preferably about 4 to 100 are desirable, and the viscosity at 25 ° C. is usually 0.1 to 1,000 mPa · s, preferably 0.5 to 500 mPa. -About s, a liquid thing is used at room temperature (25 degreeC). The degree of polymerization can be determined, for example, as number average degree of polymerization (number average molecular weight) or weight average degree of polymerization (weight average molecular weight) in terms of polystyrene in GPC (gel permeation chromatography) analysis using toluene as a developing solvent. .

Examples of the component (B) organohydrogenpolysiloxane include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris (hydrogendimethylsiloxy). Methylsilane, tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane-dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both-end trimethyl Siloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer at both ends of the molecular chain Molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpoly Siloxane, dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, both ends of molecular chain dimethylhydrogensiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, dimethylhydrogen, both ends of molecular chain Siloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer, molecular chain both ends dimethylhydrogensiloxy group-blocked methylphenylpolysiloxane, molecule And both ends endcapped with dimethyl hydrogen siloxy group diphenyl polysiloxane, in each of these exemplified compounds, those in which a part of the methyl group or entirely substituted with an ethyl group, other alkyl groups such as propyl group, the formula: R ⁵ ₃ Organosiloxane copolymer comprising a siloxane unit represented by SiO _0.5 and a siloxane unit represented by the formula: R ⁵ ₂ HSiO _0.5 and a siloxane unit represented by the formula: SiO ₂ , a siloxane unit represented by the formula: R ⁵ ₂ HSiO _0.5 And an organosiloxane copolymer composed of a siloxane unit represented by SiO ₂ , a siloxane unit represented by formula: R ⁵ HSiO and a siloxane unit represented by formula: R ⁵ SiO _1.5 or a siloxane unit represented by formula: HSiO _1.5 Organosiloxane copolymers comprising these, and these organohydrogenpolysilos The mixture which consists of 2 or more types of xane is mentioned. R ⁵ in the above formula is a monovalent hydrocarbon group other than an alkenyl group, and the same group as R ⁴ is exemplified.

  (B) The compounding quantity of a component is 1-5 mol (or piece) of silicon atom bond hydrogen atoms in (B) component with respect to 1 mol (or piece) of silicon atom bond alkenyl groups in (A) component, The amount is preferably in the range of 1 to 3 moles (or pieces). When the silicon atom-bonded hydrogen atom in the component (B) is less than 1 mole relative to 1 mole of the silicon-bonded alkenyl group in the component (A), the composition is not sufficiently cured, and this exceeds 5 moles. And the heat resistance of the silicone rubber obtained is extremely inferior.

[Component (C)]
The reinforcing silica fine powder of component (C) is not particularly limited in the type of silica and may be any material that is usually used as a rubber reinforcing material. As the reinforcing silica fine powder, those used in conventional silicone rubber compositions can be used, and in particular, reinforcing silica fine powder having a specific surface area of 50 m ² / g or more by the BET method is used. In particular, precipitated silica, fumed silica, calcined silica and the like having a specific surface area of 50 to 400 m ² / g by BET method are preferably used. Fumed silica is suitable for improving rubber strength.

  The reinforcing silica fine powder may be a surface-treated silica fine powder. In that case, these silica fine powders may be processed directly in a powder state in advance. It can be processed by a generally known technique as a normal processing method. For example, the untreated silica fine powder and the processing agent are put in a mechanical kneading apparatus or fluidized bed sealed at normal pressure, and an inert gas is present if necessary. Under the mixing treatment at room temperature or heat treatment. In some cases, a catalyst may be used to facilitate the treatment. After kneading, the treated silica fine powder can be produced by drying. The blending amount of the treatment agent may be equal to or more than the amount calculated from the coating area of the treatment agent. Treatment agents are silazanes such as hexamethyldisilazane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane. Silane coupling agents such as trimethylmethoxysilane, triethylmethoxysilane, vinyltris (methoxyethoxy) silane, trimethylchlorosilane, dimethyldichlorosilane, divinyldimethoxysilane and chloropropyltrimethoxysilane, polymethylsiloxane, organohydrogenpolysiloxane, etc. Organosilicon compounds are mentioned, and these are surface-treated and used as hydrophobic silica fine powder. As the treating agent, silane coupling agents or silazanes are particularly preferable.

  (C) The compounding quantity of a component is 1-100 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-80 mass parts, More preferably, it is 10-50 mass parts. When this component is less than 1 part by mass, the mechanical strength of the cured rubber is weakened, which may cause problems in molding such as demolding. When it exceeds 100 mass parts, filling will become difficult and workability | operativity and workability will worsen.

[(D) component]
(D) Component addition reaction catalysts include platinum black, diplatinum chloride, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and a platinum-based catalyst such as platinum bisacetoacetate. , Palladium catalyst, rhodium catalyst and the like. The addition amount of the addition reaction catalyst is a catalytic amount, and is usually 0.1 to 1,000 ppm, particularly preferably 1 to 200 ppm in terms of platinum, palladium or rhodium metal mass with respect to the component (A).

  In the silicone rubber composition of the present invention, in addition to the above components, it is optional to add other components within a range not impairing the object of the present invention.

  Other components used in the present invention include non-functional silicone oil. Non-functional silicone oil is a bleed oil component, and is a component to give the rubber part slipperiness. Depending on the application, for example, a connector that overlaps resin moldings reduces insertion force, sealability, etc. Is needed to give The non-functional silicone oil does not participate in the hydrosilylation addition reaction, and is a reactive functional group capable of crosslinking with the organopolysiloxane (A) (for example, an alkenyl group or hydrogen bonded to a silicon atom). Silicone oil that does not contain atoms (SiH groups, etc.) or other reactive functional groups in the molecule (usually the main chain is composed of repeating diorganosiloxane units, and both ends of the molecular chain are blocked with triorganosiloxy groups Linear diorganopolysiloxane).

Non-functional silicone oil has a phenyl group content (that is, mol% based on the total of monovalent organic groups bonded to silicon atoms in the organopolysiloxane (unsubstituted or substituted monovalent hydrocarbon groups), and so on). 10 mol% or more (usually 10 to 85 mol%), preferably 15 to 80 mol%, more preferably 20 to 70 mol%, thereby having good adhesion to the resin and rubber after molding The amount of bleed on the surface is sufficient, and the bleed speed is good.
The monovalent organic group (unsubstituted or substituted monovalent hydrocarbon group) bonded to the silicon atom other than the phenyl group is preferably an alkyl group having about 1 to 6 carbon atoms, particularly a methyl group.

The non-functional silicone oil has a viscosity at 25 ° C. of 100 mPa · s to 500 mPa · s, preferably 150 mPa · s to 450 mPa · s. Examples of such a phenyl group-containing silicone oil include dimethylsiloxane / diphenylsiloxane copolymer and dimethylsiloxane / methylphenylsiloxane copolymer. In particular, a straight chain is preferable, and both ends of the molecular chain are preferably blocked with a triorganosiloxy group such as a trimethylsiloxy group, a phenyldimethylsiloxy group, or a diphenylmethylsiloxy group. In the present invention, the viscosity can be measured with a rotational viscometer or the like.
The said non-functional silicone oil can be used individually by 1 type or in combination of 2 or more types.

  The amount of the non-functional silicone oil blended is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1.5 to 5 parts by weight with respect to 100 parts by weight of component (A). is there. If the amount is less than 0.5 parts by mass, sufficient oil bleedability cannot be obtained, and if it exceeds 20 parts by mass, the physical properties of the rubber may be deteriorated, which is uneconomical.

  In addition to the above-mentioned phenyl group-containing non-functional silicone oil, a non-functional silicone oil containing a trifluoropropyl group or a perfluoroalkyl ether group, a silicone-modified perfluoroalkyl ether compound, etc. are used in combination unless the above conditions are harmed. May be.

  In addition to the components described above, the silicone rubber composition of the present invention further has at least one SiH group in one molecule as an adhesion-imparting component, and an aromatic ring (for example, a phenyl group, 2 to 2 It is preferable to blend an organosilicon compound having 1 to 100, preferably 2 to 30 silicon atoms having at least one tetravalent phenylene skeleton, naphthalene skeleton, anthracene skeleton, or the like.

As the above-mentioned adhesion-imparting component, at least one, usually 1 to 20, particularly about 2 to 10 SiH groups (that is, hydrogen atoms bonded to silicon atoms) are contained in one molecule. 1 to 8, particularly 1 to 4, usually 2 to 6 and preferably 2 to 4 phenylene skeleton, epoxy group such as glycidoxy group, trimethoxysilyl group, triethoxysilyl Number of silicon atoms that may contain one or more functional groups such as a group, an alkoxysilyl group such as a methyldimethoxysilyl group, an ester group, an acrylic group, a methacrylic group, an anhydrous carboxy group, an isocyanate group, an amino group, and an amide group 1 to 100, preferably 1 to 30, more preferably 2 to 20, especially about 4 to 10 linear or cyclic organosiloxane oligomer or organoalkoxysilane. It can be exemplified an organic silicon compound such emissions.
Specific examples of such a compound include the compounds shown below.

（ｎは１〜４である。）

(N is 1-4)

から選ばれる基であり、Ｒ_w，Ｒ_xは非置換又は置換の１価炭化水素基である。ｎ＝１〜４、ｑ＝１〜５０、ｈ＝０〜１００、好ましくはｑ＝１〜２０、ｈ＝１〜５０である。）で示される基、Ｒ”は

（Ｒ_w，Ｒ_xは上記と同様であり、ｙ＝０〜１００である。）から選ばれる基であり、Ｙ’は

（Ｒ_w，Ｒ_x，ｎ，ｑ，ｈは上記と同様である。）である。ｚ＝１〜１０である。〕

R _w and R _x are each an unsubstituted or substituted monovalent hydrocarbon group. n = 1 to 4, q = 1 to 50, h = 0 to 100, preferably q = 1 to 20, and h = 1 to 50. And R ″ is a group represented by

(R _w and R _x are the same as described above, and y = 0 to 100).

(R _w , R _x , n, q, h are the same as above). z = 1-10. ]

  Furthermore, the above compound contains an alkoxysilyl group such as trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, acrylic group, methacryl group, ester group, anhydrous carboxy group, isocyanate group, amino group, amide group, etc. Organic compounds and organosilicon compounds can also be used.

The unsubstituted or substituted monovalent hydrocarbon group for R _w and R _x is preferably an alkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. In addition to those exemplified above for R ¹ and R ² , substituted monovalent hydrocarbon groups are substituted with alkoxy groups, acrylic groups, methacryl groups, acryloyl groups, methacryloyl groups, amino groups, alkylamino groups, etc. The thing which was done is mentioned.

  Moreover, this adhesion imparting component is preferably 0.001 to 0.02 mol / g, more preferably 0.002 to 0.015 mol / g, and still more preferably 0.003 to 0.010 mol / g. It is desirable to contain SiH groups.

  The adhesion-imparting component is an optional component, and its blending amount is 0 to 30 parts by mass with respect to 100 parts by mass of component (A). -20 mass parts, More preferably, it is 0.3-15 mass parts. When the amount is more than 30 parts by mass, the physical properties of the rubber may be lowered and it is uneconomical.

  The total amount of silicon-bonded hydrogen atoms (SiH groups) contained in the component (B) and the adhesion-imparting component is as follows: SiH group / alkenyl group = 1.0 to 5 with respect to the total amount of alkenyl groups in the component (A). It is preferably in the range of 0.0 (mol / mol), more preferably in the range of 1.2 to 3.0 (mol / mol).

  In addition to the above-described components, the silicone rubber composition of the present invention further includes various additives such as titanium oxide, iron oxide, cerium oxide, vanadium oxide, cobalt oxide, chromium oxide, manganese oxide and the like depending on the purpose. Metal oxide and its composites, quartz powder, diatomaceous earth, calcium carbonate, magnesium carbonate, alumina, carbon, hollow glass, hollow resin, inorganic fillers having conductivity such as gold, silver and copper, inorganic fillers such as plating powder As long as the desired properties are not impaired, pigments, heat-resistant agents, flame retardants, plasticizers, reaction control agents, and the like may be added. In addition, the addition amount of these other components can be made into a normal amount in the range which does not prevent the effect of this invention.

  The silicone rubber composition of the present invention can be obtained by simply mixing the above-described components (A) to (D) and, if necessary, other components evenly at room temperature. It is preferable to heat and heat the whole component A) or a part thereof with a planetary mixer or kneader in the range of 100 to 200 ° C. for 1 to 4 hours, cool to room temperature, and then add and mix the other components.

  The molding method can be freely selected depending on the viscosity of the mixture, and any method such as injection molding, compression molding, dispenser molding, injection molding, extrusion molding, or transfer molding may be employed. The curing condition is usually 60 to 200 ° C., particularly 80 to 160 ° C., and can be thermoformed (primary curing) within a range of 10 seconds to 24 hours, particularly 1 minute to 1 hour. In addition, about the silicone rubber hardened | cured material of this invention, you may post-cure (secondary hardening) of high temperature conditions (for example, about 2 to 6 hours at 180-220 degreeC) as needed.

  In this invention, it is preferable that the hardness (type A) prescribed | regulated by JISK6249 of the hardened | cured material formed by heat-curing the said silicone rubber composition is 20-80, especially 30-70. If the hardness is less than 20, it may be inadequate due to insufficient hardness as a sealing member for in-vehicle parts or consumer parts, and if it exceeds 80, it is inferior in elasticity as a silicone rubber used in the above applications. May end up. In order to make the hardness of the resulting cured product within this range, the alkenyl group-containing organopolysiloxane as component (A), the organohydrogenpolysiloxane as component (B), and the reinforcement as component (C) It is preferable that the amount of the fine silica fine powder blended, the crosslinking density, the molecular structure, etc. are appropriately combined in the composition according to the intended hardness.

  Moreover, in this invention, it is preferable that the tensile strength prescribed | regulated by JISK6249 of the hardened | cured material formed by heat-curing the said silicone rubber composition is 5-12 Mpa, especially 6-10 Mpa. If the tensile strength is less than 5 MPa, it may be unsuitable due to insufficient strength as a seal member for in-vehicle parts or consumer parts, and if it exceeds 12 MPa, the silicone rubber used for the above uses is inferior in elasticity. It may become. In order to make the tensile strength of the cured product within this range, as in the case of hardness, the alkenyl group-containing organopolysiloxane as the component (A) and the organohydrogenpolysiloxane as the component (B) It is preferable that the amount of the reinforcing silica fine powder as the component (C), the crosslinking density, the molecular structure, and the like are appropriately combined in the composition according to the intended tensile strength. In particular, as described above, with respect to the whole organopolysiloxane mixture (100 parts by mass) of component (A) consisting of a mixture of component (A-1) and component (A-2), component (A-1) And the mass ratio of the component (A-2) to (A-1) :( A-2) = 99.99: 0.01-80: 20, particularly 99.9: 0.1-85: 15, Is preferably blended in the composition at a ratio of 99: 1 to 90:10.

Moreover, in this invention, the 100% modulus prescribed | regulated by JISK6249 of the hardened | cured material formed by heat-curing the said silicone rubber composition is 0.1-5.0 MPa, Especially 0.5-3.5 MPa. It is preferable. If the 100% modulus is less than 0.1 MPa, the modulus may be inadequate as a sealing member for in-vehicle parts or consumer parts, and if it exceeds 5.0 MPa, the modulus is too high and the silicone used for the above applications As rubber, it may be inferior in stress relaxation. In order to set the 100% modulus of the cured product within this range, the alkenyl group-containing organopolysiloxane (A) component and the organo (B) component are the same as in the case of hardness and tensile strength. The blending amount, crosslinking density, molecular structure, etc. of hydrogenpolysiloxane and the reinforcing silica fine powder as component (C) may be appropriately combined in the composition according to the target modulus. In particular, as the component (A-2), a specific phenyl group-containing organopolysiloxane containing 1 to 30 mol%, particularly 2 to 30 mol% of a phenyl group in R ² is blended in the composition at a specific ratio. It is preferable.

  The silicone rubber composition of the present invention is also used when obtaining an integrally molded body with an organic resin. In this case, examples of the thermoplastic resin used in the present invention include ordinary olefin polymerization or condensation polymerization thermoplastic resins, such as acrylonitrile-butadiene-styrene (ABS) resin, styrene resin, Polyethylene resin, polypropylene resin, acrylic resin, polycarbonate (PC) resin, polyethylene terephthalate resin, polybutylene terephthalate (PBT) resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, nylon resin, aromatic polyamide resin, polyimide resin, A liquid crystal resin or the like, or a mixture thereof may be used.

  As a method of integrally molding the uncured silicone rubber composition having such a composition on the thermoplastic resin, the uncured silicone rubber composition is formed into a desired shape on a preformed thermoplastic resin. A method of heating at a temperature below the temperature at which the thermoplastic resin melts, a method of placing an uncured silicone rubber composition on a preformed thermoplastic resin and compressing at a temperature below the temperature at which the thermoplastic resin melts Examples include a method in which a thermoplastic resin is first injection molded into a mold by an injection molding machine, and then a silicone rubber composition is heated and injected into the mold. In addition, as an example of a method for producing a molded article of the thermoplastic resin, for example, the thermoplastic resin is pelletized and injected into a molding mold heated to a temperature higher than the softening point of the thermoplastic resin, and then the mold is molded into the thermoplastic resin. A known method of cooling below the softening point is convenient. In this case, it is possible to use devices generally called injection molding machines and transfer molding machines.

  On the other hand, the silicone rubber composition may be liquid, putty, or pasty in an uncured state, but is preferably liquid or pasty for ease of molding. In addition, the curing conditions of the silicone rubber composition according to the present invention are required to be performed at a temperature and a curing time at which the resin is not deformed, melted, or deteriorated in order to develop strong adhesiveness with the thermoplastic resin. Although it depends on the type of resin, an integrally molded body can be obtained at 100 to 150 ° C. under curing conditions of about 0.2 to 30 minutes, particularly about 0.4 to 10 minutes.

  Hereinafter, although a reference example, an example, and a comparative example are shown and the present invention is explained concretely, the present invention is not restricted to the following example. In addition, in the following example, a part and% show a mass part and mass%, respectively.

で示される分子鎖両末端がそれぞれジメチルビニルシロキシ基で封鎖された、側鎖に（即ち、主鎖を構成する２官能性シロキサン単位の一部であるジフェニルシロキサン単位として）フェニル基を有するジメチルシロキサン・ジフェニルシロキサン共重合体（Ａ−２）（ビニル価０．０００５８モル／ｇ）１０部、下記式（４）

で示されるオルガノハイドロジェンポリシロキサンＡ（ＳｉＨ量０．０１１モル／ｇ）２部、塩化白金酸の１％２−エチルヘキサノール溶液０．１部、及び反応制御剤としてエチニルシクロヘキサノールの５０％エタノール溶液０．０５部を加え、均一に約３０分混合し、シリコーンゴム組成物を得た。
このシリコーンゴム組成物を１５０℃で５分間プレスキュアして得られた硬化物より、シリコーンゴム組成物の硬化物のＪＩＳ Ｋ ６２４９で規定される硬度（タイプＡ）、引張り強さ、引裂き強さ、１００％モジュラスを評価し、結果を表１に記した。 [Reference Example 1]
70 parts of dimethylpolysiloxane (A-1) having a viscosity of 20,000 mPa · s having a viscosity of 20,000 mPa · s in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups, Use 50 parts of fumed silica with a BET specific surface area of 200 m ² / g, add 6 parts of hexamethyldisilazane, mix in a kneader mixer, mix uniformly, and then heat mix at 150 ° C. for 3 hours to form silicone. A rubber base (1) was obtained. This silicone rubber base (1) 126 parts, dimethylpolysiloxane (A-1) 20 parts, the following formula (3)

A dimethylsiloxane having a phenyl group in the side chain (that is, as a diphenylsiloxane unit that is a part of a bifunctional siloxane unit constituting the main chain), both ends of which are blocked with dimethylvinylsiloxy groups Diphenylsiloxane copolymer (A-2) (vinyl value 0.00058 mol / g) 10 parts, following formula (4)

2 parts of organohydrogenpolysiloxane A (SiH amount 0.011 mol / g), 0.1 part of 1% 2-ethylhexanol solution of chloroplatinic acid, and 50% ethanol of ethynylcyclohexanol as a reaction control agent 0.05 part of the solution was added and mixed uniformly for about 30 minutes to obtain a silicone rubber composition.
From the cured product obtained by press-curing this silicone rubber composition at 150 ° C. for 5 minutes, the hardness (type A), tensile strength, tear strength of the cured product of the silicone rubber composition as defined by JIS K 6249 100% modulus was evaluated and the results are shown in Table 1.

[Example 1]
126 parts of the silicone rubber base (1) of Reference Example 1, 20 parts of dimethylpolysiloxane (A-1) blocked with both ends of the molecular chain of Reference Example 1, and dimethylvinylsiloxy group with both ends of the molecular chain of Reference Example 1 10 parts of a blocked dimethylsiloxane / diphenylsiloxane copolymer (A-2), 2 parts of the organohydrogenpolysiloxane A of Reference Example 1, a viscosity of 450 mPa · s at 25 ° C. and a phenyl group content of 30 mol%. 2.5 parts of a dimethylsiloxane / diphenylsiloxane copolymer blocked with a siloxy group, a dimethylsiloxane / diphenyl having a viscosity of 160 mPa · s at 25 ° C. and a phenyl group content of 60 mol%, both ends blocked with a trimethylsiloxy group 2.5 parts of siloxane copolymer, 1% 2-ethylhexanol solution of chloroplatinic acid .1 parts, and 50% ethanol solution and 0.05 part of ethynyl cyclohexanol was added as a reaction control agent, were uniformly mixed for about 30 minutes to obtain an oil-bleeding silicone rubber composition.
The results of measuring the rubber physical properties of this oil-bleedable silicone rubber composition in the same manner as in Reference Example 1 are shown in Table 1.

で示されるフェニレン骨格を有する接着助剤Ａ（ＳｉＨ量０．００７９モル／ｇ）１．０部、塩化白金酸の１％２−エチルヘキサノール溶液０．１部、及び反応制御剤としてエチニルシクロヘキサノールの５０％エタノール溶液０．０５部を加え、均一に約３０分混合し、オイルブリード性シリコーンゴム接着剤組成物を得た。
このオイルブリード性シリコーンゴム接着剤組成物のゴム物性を参考例１と同様に測定した結果を表１に記した。 [Example 2]
126 parts of the silicone rubber base (1) of Reference Example 1, 20 parts of dimethylpolysiloxane (A-1) blocked with both ends of the molecular chain of Reference Example 1, and dimethylvinylsiloxy group with both ends of the molecular chain of Reference Example 1 10 parts of a blocked dimethylsiloxane / diphenylsiloxane copolymer (A-2), 2 parts of the organohydrogenpolysiloxane A of Reference Example 1, a viscosity of 450 mPa · s at 25 ° C. and a phenyl group content of 30 mol%. 2.5 parts of a dimethylsiloxane / diphenylsiloxane copolymer blocked with a siloxy group, a dimethylsiloxane / diphenyl having a viscosity of 160 mPa · s at 25 ° C. and a phenyl group content of 60 mol%, both ends blocked with a trimethylsiloxy group 2.5 parts of siloxane copolymer, the following formula (5)

1.0 part of adhesion promoter A having a phenylene skeleton represented by formula (SiH amount 0.0079 mol / g), 0.1 part of a 1% 2-ethylhexanol solution of chloroplatinic acid, and ethynylcyclohexanol as a reaction control agent A 50% ethanol solution of 0.05 part was added and mixed uniformly for about 30 minutes to obtain an oil-bleeding silicone rubber adhesive composition.
The results of measuring the rubber physical properties of this oil-bleedable silicone rubber adhesive composition in the same manner as in Reference Example 1 are shown in Table 1.

で示されるビニルメチルシロキサン単位として）ビニル基を有するジメチルポリシロキサン（Ａ−１’）（重合度１８０、ビニル価０．０００５８モル／ｇ）１０部に変更した組成物を、均一に約３０分混合し、シリコーンゴム組成物を得た。
このシリコーンゴム組成物のゴム物性を参考例１と同様に測定した結果を表１に記した。 [Comparative Example 1]
In Reference Example 1, instead of 10 parts of the dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group having a phenyl group, both ends of the molecular chain were blocked with a trimethylsiloxy group. In the side chain (that is, as a part of the bifunctional siloxane unit constituting the main chain, the following formula

The composition changed to 10 parts of dimethylpolysiloxane (A-1 ′) having a vinyl group (polymerization degree 180, vinyl value 0.00058 mol / g) as a vinylmethylsiloxane unit represented by By mixing, a silicone rubber composition was obtained.
The rubber physical properties of this silicone rubber composition measured in the same manner as in Reference Example 1 are shown in Table 1.

で示されるビニルメチルシロキサン単位として）ビニル基を有するジメチルポリシロキサン（Ａ−１’）（重合度１８０、ビニル価０．０００５８モル／ｇ）１０部に変更した組成物を、均一に約３０分混合し、オイルブリード性シリコーンゴム組成物を得た。
このオイルブリード性シリコーンゴム組成物のゴム物性を参考例１と同様に測定した結果を表１に記した。 [Comparative Example 2]
In Example 1, instead of 10 parts of a dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group having a phenyl group, both ends of the molecular chain were blocked with a trimethylsiloxy group. In the side chain (that is, as a part of the bifunctional siloxane unit constituting the main chain, the following formula

The composition changed to 10 parts of dimethylpolysiloxane (A-1 ′) having a vinyl group (polymerization degree 180, vinyl value 0.00058 mol / g) as a vinylmethylsiloxane unit represented by An oil bleedable silicone rubber composition was obtained by mixing.
The results of measuring the rubber physical properties of this oil-bleedable silicone rubber composition in the same manner as in Reference Example 1 are shown in Table 1.

で示されるビニルメチルシロキサン単位として）ビニル基を有するジメチルポリシロキサン（Ａ−１’）（重合度１８０、ビニル価０．０００５８モル／ｇ）１０部に変更した組成物を、均一に約３０分混合し、オイルブリード性シリコーンゴム接着剤組成物を得た。
このオイルブリード性シリコーンゴム接着剤組成物のゴム物性を参考例１と同様に測定した結果を表１に記した。 [Comparative Example 3]
In Example 2, instead of 10 parts of the dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group having a phenyl group, both ends of the molecular chain were blocked with a trimethylsiloxy group. In the side chain (that is, as a part of the bifunctional siloxane unit constituting the main chain, the following formula

The composition changed to 10 parts of dimethylpolysiloxane (A-1 ′) having a vinyl group (polymerization degree 180, vinyl value 0.00058 mol / g) as a vinylmethylsiloxane unit represented by An oil bleedable silicone rubber adhesive composition was obtained by mixing.
The results of measuring the rubber physical properties of this oil-bleedable silicone rubber adhesive composition in the same manner as in Reference Example 1 are shown in Table 1.

で示される分子鎖両末端がそれぞれジメチルビニルシロキシ基で封鎖された側鎖に（即ち、主鎖を構成する２官能性シロキサン単位の一部であるジフェニルシロキサン単位として）フェニル基を有するジメチルシロキサン・ジフェニルシロキサン共重合体（Ａ−２’）（フェニル基含有量５．５モル％、ビニル価０．００００７モル／ｇ）３０部、参考例１のオルガノハイドロジェンポリシロキサンＡ２部、塩化白金酸の１％２−エチルヘキサノール溶液０．１部、及び反応制御剤としてエチニルシクロヘキサノールの５０％エタノール溶液０．０５部を加え、均一に約３０分混合し、シリコーンゴム組成物を得た。
このシリコーンゴム組成物のゴム物性を参考例１と同様に測定した結果を表１に記した。 [Comparative Example 4]
In 126 parts of the silicone rubber base (1) of Reference Example 1, the following formula (6)

A dimethylsiloxane having a phenyl group in a side chain blocked with a dimethylvinylsiloxy group at both ends thereof (that is, as a diphenylsiloxane unit that is a part of a bifunctional siloxane unit constituting the main chain) 30 parts of diphenylsiloxane copolymer (A-2 ′) (phenyl group content 5.5 mol%, vinyl value 0.00007 mol / g), 2 parts of organohydrogenpolysiloxane A of Reference Example 1, chloroplatinic acid 0.1 parts of a 1% 2-ethylhexanol solution and 0.05 parts of a 50% ethanol solution of ethynylcyclohexanol as a reaction control agent were added and mixed uniformly for about 30 minutes to obtain a silicone rubber composition.
The rubber physical properties of this silicone rubber composition measured in the same manner as in Reference Example 1 are shown in Table 1.

で示される分子鎖両末端がそれぞれジメチルビニルシロキシ基で封鎖された側鎖に（即ち、主鎖を構成する２官能性シロキサン単位の一部であるジフェニルシロキサン単位として）フェニル基を有するジメチルシロキサン・ジフェニルシロキサン共重合体（Ａ−２”）（フェニル基含有量０．５モル％、ビニル価０．００００８モル／ｇ）１０部、参考例１のオルガノハイドロジェンポリシロキサンＡ２部、塩化白金酸の１％２−エチルヘキサノール溶液０．１部、及び反応制御剤としてエチニルシクロヘキサノールの５０％エタノール溶液０．０５部を加え、均一に約３０分混合し、シリコーンゴム組成物を得た。
このシリコーンゴム組成物のゴム物性を参考例１と同様に測定した結果を表１に記した。 [Comparative Example 5]
To 126 parts of the silicone rubber base (1) of Reference Example 1, 20 parts of dimethylpolysiloxane (A-1), the following formula (7)

A dimethylsiloxane having a phenyl group in a side chain blocked with a dimethylvinylsiloxy group at both ends thereof (that is, as a diphenylsiloxane unit that is a part of a bifunctional siloxane unit constituting the main chain) Diphenylsiloxane copolymer (A-2 ″) (phenyl group content 0.5 mol%, vinyl value 0.00008 mol / g) 10 parts, organohydrogenpolysiloxane A 2 parts of Reference Example 1, chloroplatinic acid 0.1 parts of a 1% 2-ethylhexanol solution and 0.05 parts of a 50% ethanol solution of ethynylcyclohexanol as a reaction control agent were added and mixed uniformly for about 30 minutes to obtain a silicone rubber composition.
The rubber physical properties of this silicone rubber composition measured in the same manner as in Reference Example 1 are shown in Table 1.

Claims (6)

(A) The following average composition formula (1)
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ represents an alkenyl group, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is a positive number satisfying 0.0001 to 0.2. Yes, b is a positive number satisfying 1.7 to 2.2, provided that a + b is a positive number satisfying 1.9 to 2.4.
An organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having two different organopolysiloxanes (A-1) and (A-2) having different compositions Among the two types of organopolysiloxanes contained in the organopolysiloxane mixture, the (A-1) component does not contain a phenyl group in R ² in the average composition formula (1). The component (A-2) is an organopolysiloxane containing 1 to 30 mol% of a phenyl group in R ² in the average composition formula (1), and the components (A-1) and (A-2) ) Mixture in which the mass ratio to the component is (A-1) :( A-2) = 99.9: 0.1-85: 15 (100 in total): 100 parts by mass,
(B) The following average composition formula (2)
_{^{R 4 d H e SiO (4}} -de) / 2 (2)
(In the formula, R ⁴ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, d is 0.7 to 2.1, e is 0.001 to 1.0, and d + e is 0. A positive number satisfying .8 to 3.0.)
And an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule: the number of hydrogen atoms bonded to the silicon atoms contained in this component is the silicon atom in component (A) An amount of 1 to 5 per bonded alkenyl group,
(C) Reinforcing silica fine powder: 1 to 100 parts by mass,
(D) addition reaction catalyst: catalyst amount,
(E) 20 to 70 mol% of monovalent organic groups bonded to silicon atoms in the organopolysiloxane are phenyl groups, and monovalent organic groups bonded to silicon atoms other than phenyl groups are 1 to 6 carbon atoms. A non-functional silicone oil having a viscosity at 25 ° C. of 150 to 450 mPa · s as measured by a rotational viscometer: 0.5 to 20 parts by mass, and the above (A− The viscosity at 25 ° C. of component (A) comprising a mixture of 1) component and (A-2) component is 50 to 100,000 mPa · s as measured by a rotational viscometer, and 25 of component (A-2) A silicone rubber composition having a viscosity at 50 ° C. measured by a rotational viscometer of 50 to 1,000 mPa · s is prepared, and the composition is heat-cured, as defined in JIS K 6249 of a cured silicone rubber. 100% A method of reducing the Jurasu.   Further, (F) an organosilicon compound having at least one SiH group and at least one phenylene skeleton in one molecule is used as an adhesion-imparting component, and 0.1 to 30 masses per 100 mass parts of component (A). The method of claim 1 containing parts. The method according to claim 2, wherein the adhesion-imparting component is selected from compounds represented by the following formula.

(N is 1-4) (A) The following average composition formula (1)
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ represents an alkenyl group, R ² represents an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is a positive number satisfying 0.0001 to 0.2. Yes, b is a positive number satisfying 1.7 to 2.2, provided that a + b is a positive number satisfying 1.9 to 2.4.
An organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule and having two different organopolysiloxanes (A-1) and (A-2) having different compositions Among the two types of organopolysiloxanes contained in the organopolysiloxane mixture, the (A-1) component does not contain a phenyl group in R ² in the average composition formula (1). The component (A-2) is an organopolysiloxane containing 1 to 30 mol% of a phenyl group in R ² in the average composition formula (1), and the components (A-1) and (A-2) ) Mixture in which the mass ratio to the component is (A-1) :( A-2) = 99.9: 0.1-85: 15 (100 in total): 100 parts by mass,
(B) The following average composition formula (2)
_{^{R 4 d H e SiO (4}} -de) / 2 (2)
(In the formula, R ⁴ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, d is 0.7 to 2.1, e is 0.001 to 1.0, and d + e is 0. A positive number satisfying .8 to 3.0.)
And an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule: the number of hydrogen atoms bonded to the silicon atoms contained in this component is the silicon atom in component (A) An amount of 1 to 5 per bonded alkenyl group,
(C) Reinforcing silica fine powder: 1 to 100 parts by mass,
(D) addition reaction catalyst: catalyst amount,
(E) 20 to 70 mol% of monovalent organic groups bonded to silicon atoms in the organopolysiloxane are phenyl groups, and monovalent organic groups bonded to silicon atoms other than phenyl groups are 1 to 6 carbon atoms. A non-functional silicone oil having a viscosity at 25 ° C. of 150 to 450 mPa · s as measured by a rotational viscometer: 0.5 to 20 parts by mass, and the above (A− The viscosity at 25 ° C. of component (A) comprising a mixture of 1) component and (A-2) component is 50 to 100,000 mPa · s as measured by a rotational viscometer, and 25 of component (A-2) A silicone rubber composition having a viscosity at 50 ° C. of 50 to 1,000 mPa · s as measured by a rotational viscometer.   Further, (F) an organosilicon compound having at least one SiH group and at least one phenylene skeleton in one molecule is used as an adhesion-imparting component, and 0.1 to 30 masses per 100 mass parts of component (A). The silicone rubber composition according to claim 4 containing parts. The silicone rubber composition according to claim 5, wherein the adhesion-imparting component is selected from compounds represented by the following formula.

(N is 1-4)